Novel quaternary ammonium compounds and methods of producing them



in smcoating textiles for various purposes.

United States Patent 0 This invention relates to new monomeric andpolymeric quaternary ammonium compounds and to their produc-' tion. Itis particularly concerned with the production of monomers and polymers,either homopolymers or copolymers, comprising units containing in abranch thereon quaternary ammonium nitrogen to which is attached a M vradical containing carbonamido or ureido groups, which;

polymers are water-soluble or readily water-dispersible but by virtue ofthe amide or ureido groups are convert ible to an insoluble condition.Such polymers have a wide variety of uses as will be pointed out moreparticularly hereinaften. They are particularly useful as adjuvants topaper for imparting in-' creased wet strength and as agents forimpregnating or fact that they are readily converted to insolublecondition after incorporation in the paper or textile, they may berendered resistant to removal therefrom during subsequent wetting,washing or scouring operations.

The polymeric compounds of the present invention are water-soluble oreasily water-dispersible addition polymers of monoethylenical-lyunsaturated monomers comprising at least 5 mole percent, and preferablyat least 30 mole percent, of at least one monomer of the presentinvention 3 having the structure of Formula I:

where R is hydrogen or methyl,

A is a straight-chain or branched-chain alkylene group having 2 to 10carbon atoms which may be sub stituted by one or more hydroxyl groups,at least two of the carbon atoms thereof being'connected in a chain'-between the N atom and Y group of the formula, R and R may be (1)separate groups selected individ-ually from the group consisting ofsaturated and ethylenically unsaturated hydrocarbon groups of 1 to 4carbon atoms, and (2) a single group selected from the R is selectedfrom radicals having the structureof one of Formulas and III following.

wherein m is an integer: having a value of 1 to 2,'

R is selected from H, -CH OH, and CI-I OR where 7 R is an alkyl grouphaving from 1 to 4 carbon atoms,

' p is an integer having a value 0t 1 to 2,

Because of the 2 3,008,851 Patented Nov. 14, 1961 ice - It is an integerhaving a value of '1 to 2 when p is 2 but having only a value of 1 whenp is 1, and

Z is selected from and-CH when p is l, but isonly CH when p is 2. Thus,R may have the structures of the following Formulas IV, V, VI, VII,VIII, and IX:

- Wherem is 1;

when n is 1, p is l, andZis when n is 2,1) is 2, and Z is CH Anessential characteristic. of the polymers of the in-' vention is theircapability of being cured to an insoluble condition and this isattributable to the R substituent. When R is H, formaldehyde may bereacted with the polymer to produce the corresponding methylolderivative, or, when a lower alcohol is also present, the correspondingalkoxymethyl ('CH OR derivative, either of which are convertible to aninsoluble condition on heating in the presence of an acidiclcatalyst.

The polymers may contain up to 70% byweight of one or more othercomonomers such as acrylonitrile, the vinyl aromatic compounds, moreparticularly the vinyl aromatic hydrocarbons (e.g., styrene, isopropenyltoluene, the various dia-lkyl styrenes, etc), other aliphatic compoundscontaining a CH =C= grouping, e.g. the various substitutedacrylonitriles (e.g., methacrylonitrile, ethacrylonitrile,phenyla-crylonitrile, etc.), acrylamide and the various substitutedacrylarnides (e.g., methacrylamide, ethacrylamide, the variousN-substituted acrylarnides which are ditferent from those used inpracticing the present invention and the various N-substitutedalk-acrylamides, for instance N-methylol acrylamide, N-monoalky-l ,and-dialkyl acrylarnides and methacrylamides, e.g. N-monomethyl, -ethyl,-propyl, -butyl, etc. and N-dimethyl, -ethyl, -propyl, -butyl, etc.,acrylarnides and methacrylamides, N-monoaryl and -diaryl acrylarnidesand alkacrylamides, e.g., N-monophenyl and -diphenyl acrylarnides andmethacrylamides, etc.),

3 vinyl esters, e.g., vinyl acetate, vinyl propionate, vinyl butyrate,vinyl isobutyratc, yinyl v-alerate, etc., esters of an acrylic acid(including acrylic acid itself and the various rat-substituted acrylicacids, e.'g., methacrylic acid, ethacrylic acid, phenylacrylic acid,etc.), more particularly the alkyl esters of an acrylic acid, elg theethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,amyl, hexyl, heptyl, octyl, decyl, dodecyl, etc. esters of acrylic,methacrylic, ethacrylic, phenylacrylic, etc. acids, vinyl ethers, suchas butyl' vinyl ether, N-vinyl compounds such as N-vinyl pyrrolidone,and olefins, such as ethylene, fiuorinated vinyl compounds, such asvinylid'ene fluoride, as well as other vinylaromatic and vinyl aliphaticcompounds, and other compounds containing a single CH =C= grouping.

If the polymer contains less than 30 mole percent of quaternary nitrogencontaining units of Formula I, it preferably contains enough additionalquaternary 'nitrogen containing units of other types to provide a totalof at least 30 mole percent of quaternary nitrogen containing groups.Examples of other such units are those having the structure of FormulaIa:

where the symbols have the same definition as before and R may bebenzyl, cyclohexyl, or an alkyl group having 1 to 4 carbon atoms.

Those polymers of the invention in which the R and R groups aresaturated may be made by first polymerizing or copolymerizing a'naminehaving the structure of Formula X: Y

where R, Y, and A are the same as defined above and R and R may be (1)separate groups selected individually from the group consisting ofsaturated hydrocarbon groups of 1 to 4 carbon atoms, and (2) a singlegroup selected from the rrrorp'holino'residu'e :(CQHQ O, the pyrrolidinoresidue -C.,H the piperidino residue C H and an N -alkyl piperazinoresidue I I 2 I btR' where R is an alkyl group of l to 18 carbon atoms,such as methyl, ethyl, isopropyl. Then in the polymer thereby obtainedpart or all of the tertiary nitrogen groups are quaternized by means ofan alkylating agent of the Formula R with or without an alkyl'atingagent R X, to provide at least 30% by weight of quaternized monomericunits in the polymer including at least 5 mole percent of units havingthe Formula I-.

An alternate procedure to produce the polymers of the present inventionin which R and R are saturated is to quaternize corresponding monomersof Formula X with R ,X-, with or without R X, or one of such monomerswith R X and another with R X, and then to polymerize or copolyrnerizethe quaternary ammonium compounds obtained which have the structure ofFormulas Xa and Xb:

Y-AN. 9a where the symbols have *the'saine definitions'as before.

Any known procedure for polymerizing the compounds may be employedeither for poly'rnerizin'g' the amine or amines before quaternization orfor polymerizing the quater'ni'zed monomer or monomers. For example,vari- 4 nitri-le. Suchcatalysts may be employed for polymerization inbulk or in solution. On the other hand, if polymerization is to beeffected in emulsions or dispersions of the monomers, ammoniumpersulfate or alkali metal persulfates may be employed. Polymerizationmay be effected at 60 to 100 C. and thearnount of catalyst or initiatormay be from 0.1% to about 20% by weight of themonomer or monomers.Polymerization may be carriedo'ut in an inert atmosphere such asnitrogen.

The quaterni'zation of the monomer; or monomers, or of the polymer ispreferably effected in a polar solvent such as water, ethanol,acetonitrile, dimethy-lformamide, or glycol ethers such as ethoityethylhydroxyethyl ether or mixtures of one of thesesolvents with benzene ortoluene at a temperature of 60- C. to 100 C. for a period or about twoto twelve hours. The alkyla'tin'g agent RX may be used in a quantitythat is molarly equivalent to the total number of amine groups in thepolymer to quaternize all of such groups. However, when there is morethan 5 mole percent of the monomeric units containing a quaternizableamine group, it is unnecessary to quaternize all of such amine groupsand the amount of quaternizing agent may be less than the amountrequired to quaternize all of the amine groups in the polymer providedsufiicint is used to provide 5 mole percent of quaternized monomericunits having the structure of Formula I in the final polymer.

The molecular weight of thefinal quaternized polymer is not critical. Itmay vary from as fevv 'as 10 monomeric units to a molecular weight ofthe order of 500,000 or more.

One procedure for producing polymers containing uni-ts of the formulaCur o R R (where R, A, R, and R are as defined above and Y is -CONR-)and adapted to be quaternized as described above to produce the polymersof the invention is to aminolyze polymers of an ester of acrylic ormethacrylic acid, preferably poly(methyl acrylate) or a copolymer of atleast 5 mole percent, and preferably at least 30 mole percent of methylacrylate, by means of at least one amine of Formula XI:

where the symbols are the same as defined above. Geherally, aminolysisisperformed in a medium which is anhydrous or contains but little waterunless considerable carbonyl groups are "desired in the final polymericprodnet. The amine or amine mixture itself may serve as the solventjaswell as the reactant for amino-lyz'ing the polymerized methyl acrylateand am-inolysis may be er fec't'ed' at temperatures of 90 to 130 C. in atime of '96 hours to 24 hours respectively, the time required generallybeing inversely proportional to the temperature. In the presence of a 3to-4 fol'd excess of amine, complete nolysis may be effected in thetimes and the temperatu'res just mentioned, and it has'been found thatthe higher the temperature employed, the higher is the final molecularweight of polymer obtained. A catalyst to accelerate the reaction isunnecessary but an alkoxide such as sodium ous free radical catalystsmay be used such as hydrogen peroic id'e, organic peroxide, such asbutyl perbenzoate or benzyl peroxide or am catalysts such as'azodiisobutyromethoxide, sodium ethoxide, or the like, may be used inamounts of from /2% to 20% by weight of the polymer. With acatalyst, anamount of the amine or amine mixture equivalent to the ester groups tobe aminolyzed maybe dissolved in a solvent such as toluene or additionalarnine, either'the same or different, or an alcohol, such as methanol,ethanol, or butanol, and the complete aminolysis may be obtained ineight hours at a temperature of to An advantageous systemis to start intoluene in which the polymerized ester is soluble and during thereaction to add an alcohol such as methanol, ethanol, or butanol inwhich the amifiolyzed polymer is soluble, and subsequently toremove-the. solvent to obtain the final polymer.

The polymeric esters of. alcohols other than methyl, such as of ethylalcohol, propyl alcohol, butyl alcohol, and so on, require an increasein the time and temperature factor to produce a corresponding conversionof ester groups to amido groups in the polymer. Generally, when an amineused'contains a primary nitrogen atom, it is necessary to maintain thereaction medium containing the polymeric ester and amine at atemperature below 130 C. in order to avoid imide formation withconsequent cross-linking and insolubilizat-ion of the final polymer.However, when theaminolysis is effected by amines containing secondarynitrogen atoms but no primary nitrogen atom, there is no possibility ofcross-linking or irnide formation so that higher temperatures may beused up to 180 to 200 C.

Polymerized esters of the unsaturated acids in which the a-carbon atomis substituted by an alkyl group, such as methyl, ethyl, propyl, orisopropyl, of which methyl methacrylate, methyl ethylacrylate and methylpropylacrylate are typical, are more difiicult to aminolyze and when anamine containing a primary nitrogen atom is used, it is difficult to getaminolysis of 60% to 100% of the ester groups without cross-linking.Generally, however, the aminolysis may be eifected at temperatures of180 to 200 C. for three to seven hours with production of uncross-linkedproducts which are up to 60% aminolyzed. Generally to get a largerproportion of the ester groups or all thereof in the polymer aminolyzed,a to -fold excess of amine may be reacted at a temperature of 130 C. fora time of from four to seven days. Alternatively. an alkoxide catalystmay be used with- 2-to-4- fold excess amine or an amount of amineequivalent to the ester groups to be aminolyzed may be used at 130 C.

As the alkyl substituent on the a-carbcn of the acrylic acid increasesin size, more drastic conditions are generally required. Similarly, asthe alkyl group of the ester increases in size, more drastic conditionsare necessary to elfect aminolysis; thus, when polymerized methylmethacrylate is replaced with polymerized ethyl methacrylate, longertimes and higher temperature must be used. As already stated, imideformation may be prevented by the use of amines which contain asecondary nitrogen atom but no primary nitrogen atom.

The difference in reactivity of thesevarious esters makes it possible toobtain for all practical purposes a selective aminolysis of copolymerscontaining difierent ester units. For example, when the final quaternaryammonium compound desired to be produced is one containing methylmethacrylate as comonomer units, a copolymer of methyl methacrylate withat least 5 mole percent of methyl acrylate may serve as a startingmaterial, so that aminolysis converts the ester groups of the methylacrylate units to amide units without afiecting the ester units ofthe'methyl methacrylate to any considerable extent. Such an aminolysis,for example, may be effected at 80 to 120 C. in the presence of anamount of an amine mixture which is equivalent to the ester groups inthe methyl acrylate portion of the copolymer. Similarly, if it isdesired to produce a copolymer containing quaternary ammonium groupswith one or more comonomers of non-ester type listed hereinabove such asof styrene, a corresponding copolymer, as of styrene and methylacrylate, may be used as the starting material in which the proportionof acrylate units corresponds to the number of acrylamide units desiredand all such acrylate units may be converted to amide groups in theaminolysis.

To produce polymers of Formula I in which R has the specific structureof Formula IV, a-chloroacetamide, or itsv methylol or alkoxymethylderivatives may be used to quaternize an amine of Formula X.

To produce polymers cfFormula I in which R hasthe specific structure ofFormula V, an amine of Formula X is quaternized by an alkylating agentobtained by reacting wchloroacetyl chloride with urea as described inJ.A.C.S., vol. 61, p. 1377. The resulting a-chloroacetylurea'may bereacted with formaldehyde, with or without a lower alcohol, to producethe corresponding methylol or alkoxymethyl derivative before using it toquaternize the amine. To produce polymers of Formula I in which R hasthe specific structure of Formula VI, an amine ofFormula X isquaternized by N-(u-chloroacetyl)-N,N'-ethyleneurea prepared by reactinga-chloroacetyl chloride with N,N'-ethyleneurea at 60 to C. in toluene.The quaternizing agent thus prepared, may, if desired, be reacted withformaldehyde, with or without a lower alcohol, to produce thecorresponding methylol or alkoxymethyl derivative before using it toquaternize the amine.

, To produce polymers of Formula I in which R has the specific structureof Formula VII, an amine of Formula Xis quaternized by theN-(p-chloroethyl)-N,N.- ethyleneurea obtained by reacting thionylchloride (SOCI with N -(fl-hydroxyethyl)-N,N-ethyleneurea. Thequaternizing agent thus prepared may, if desired, be reacted withformaldehyde, with or without a lower alco hol, to producethecorresponding methylol or alkoxymethyl derivative before using it toquaternize the amine. To produce polymers of Formula I in which'R hasthe specific structure of Formula VIII, an amine of Formula X isquaternized by the N- [fi-(a-chloroacetamido)- ethy1]-N,N-ethyleneureaobtained by reacting methyl achloroacetate withN-(B-aminoethyl)-N,N'-ethy1eneurea. The quaternizing agent thus preparedmay, if desired, be reacted with formaldehyde, with or without a loweralcohol, to produce the corresponding methylol or alkoxymethylderivative beforeusing it to quaternize the amine. To produce polymersof Formula I in which R has the specific structure of Formula IX, anamine of For mula X is quaternized by the N-[3.-(a-chloroacetamido)-propyl] -N,N'-trimethyleneurea obtained by reactingmethyla-chloroacetate with N-(3-aminopropyl)-N,Nf-trimeth yleneurea. Thequaternizing agent thus prepared may, if desired, be reacted withformaldehyde, with or without a lower alcohol, to produce thecorresponding methylol or alkoxymethyl derivative before using it toquaternize the amine. The new compounds are viscous to solid resinousmaterials of water-soluble character or at least readilywaterdispersible character. They are generally also soluble in organicsolvents of polar type, such as alcohols, especially the lower alcohols,methanol, ethanol, propanol, isopropanol and the butyl alcohols, andalso in acetonitrile, dimethylformamide and so on. When the polymersarefree of units containing carboxyl or free amine groups, they aregenerally substantially neutral. The polymeric com-' pounds of thepresent invention can be isolated byany of numerous conventionalprocedures, such as by freeze-dry-' ing, evaporation of solvents fromthe reaction mixtures containing them, or the like. Those polymericcompounds in which R is hydrogen are quite stable under normal storageconditions but are capable of reacting with formaldehyde as well asother aldehydes, protein, enzymes, and polyacids. Thus, the polymers mayserve as precipitants for proteins and enzymm and mayv be reacted withpolycarboxylic acids'to form gels which are revertible to sols on changeof pH. Reaction with formaldehyde in an aqueous medium may be effectedreadily on the alkaline side between pH of 8 and 9when the sub.-stituent R contains a ureido group and from a pH of 9 to 10 when theradical R comprises a simpleamide linkage. The reaction is generallycarried out in the presence of l to 3 moles of formaldehyde per amide'or ureido group, an alkali metal. hydroxide being employed to providethe necessary pH value; The reaction may be elfected in the presence ofa lower alcohol, to provide the alkoxymethyl derivative, at atemperature of 60 to 80 C. for one-half to two hours. Alkoxymethylationmay .be effected in two stages wherein the first stage ;is carried andthe second stage is effected under acid conditions at a pH between 3 and4.

The alkoxymethylated derivatives are preferable to the simplemethylolated derivatives in that the former are more stable under normalconditions of storage.

Those compounds in which R is hydrogen are useful as b'actericides,fungicides, and insecticides. They are particularly valuable asbactericidal fungicides which are effective in hard water. They may beused as additives to film-forming solutions adapted to be spun orextruded into filrris, sheets or fibers, such as those of celluloseacetate, polyvinyl alcohol, polyvinyl pyrrolidone, nylon, oracrylonitrile polymers for the purpose of modifying the properties ofthe product especially their moisture-regain properties, their feel orhandle, their solubility, and their affinity for dyes. After theextrusion or spinning of such films or fibers, the drying stage couldinclude or be followed by a treatment with formaldehyde, glyoxal orother aldehyde with an acid catalyst such as ammonium chloride andbaking or curing operation to convert the polymer to an insolublepermanent condition. They are useful as dispersants when they have lowmolecular weights such as from 1000 to 5000. They are also useful asflocculants for suspended matter in water purification and theconcentration of ores or the like when they have molecular weights of50,000 or higher, preferably at least 100,000. They may be applied totextiles for various purposes. When they comprise a substantialhydrophobic component as in the radical A or in the comonomers whencopolymers are used, they may serve as water-repellent or water-proofingcoating compositions. Those which do not comprise a markedly highhydrophobic component may be applied as antistatic agents to hydrophobictextiles such as those comprising fibers, filaments or yarns ofcellulose esters, such as cellulose acetate, polyesters such aspolyethylene terephthalate (Dacron) and vinyl polymers, such as thosecontaining 75% to 95% of vinyl chloride, acrylonitrile, or the like(including the acrylonitrile copolymers now available under thetradenames Orlon and Acrilan). They may also be -incorporated in paper,for example as a beater additive, for imparting high Wet strength orother desirable properties'to the paper. They may be applied to leatherand other substrates, for various purposes including waterr'epellency,prevention of the development of static electricity and the like. In allof such applications, they may be employed either as temporaryconditioning agents or they may be converted into durable finishes byreaction with formaldehyde or other reactive material in eluding othertypes of aldehydes to convert them to insoluble condition through theagency of the carbonamido or urei'do group in the radical R of thecompounds. When so reacted with the aid of an acidic catalyst with orwithout elevated temperatures, the polymeric compounds of the presentinvention become permanently affixed to the substrate and resist removalduring subsequent operations of washing, scouring, and in many casesdry-cleaning. It is believed that in the case of certain types ofsubstrates, particularly the cellulosic types and the proteinous types,such as rayon or wool respectively, there is also reaction between thesubstrate, the polymer and the other reactants such as formaldehyde, butit is not intended to be limited to any particular theory of operationtherein.

Those polymers in which the group R is methylol or alkoxymethyl, such as:methcxymethyl, already con"- tain a reactive element adapting them tobe converted into durable components of any system to which they areapplied. Thus, these readily water-dispersible polymeric compounds areeasily applied through aqueous or alcoholic media to various substratesincluding those of paper, leather,- textiles or the like and are adaptedto be converted to insoluble condition merely by heating preferably inthe presence of an acidic catalyst which may be incorporated onto thesubstrate at thesame time as it is impregnated with the polymericcompounds of the present invention. Thus, substrates of wool, cellulose,rayon, Cellophane, cotton, cellulose esters, such as cel lulose acetateor cellulose acetate butyrate, polyvinyl alcohols, polyamides of thenylon type, homopolymers or copolymers of acrylamide or methacrylamide,may be impregnated or coated with solutions of the polymers of thepresent invention in which the group R is a methylol or an alkoxymethylgroup and a small amount, from /z% to 2%, on the Weight of the compoundof the present invention, of an acidic catalyst and after drying, thetreated substrate may be subjected to baking or curing operations inwhich the polymer applied is converted to an insoluble condition whichmay or may not involve reaction with the substrate as well. As an acidiccatalyst there may be used hydrochloric acid, sulfuric acid, phosphoricacid, oxalic acid, ammonium phosphate, ammonium thiocyanate,hydrochloric or other acid salts of a hydroxy aliphatic amine including2-methyl-2-amino-l-propanol, 2-methyl-2-amino-1,3-prop'andiol,tris(hydroxymethyl)-aminomethane, 2-phenyl-2- amino-l-propanol,Z-methyl-Z-amino-l-pentanol, Z-aminobutanol, triethanolamine,2-amino-2-ethyl-l-butanol, also ammonium chloride, pyridinehydrochloride, benzyl dimethylamine oxalate. v

Thus, the compounds'may be applied to hydrophobic textile materials ofthe types mentioned above in an amount of 2% to 10% on the weight of thetextile material to provide an antistatic finish which can be convertedto insoluble condition by drying and baking or curing at a temperatureof 240 to 450 F. for periods of time which are inversely proportional tothe temperature, such as for a period of about 30 minutes at 240 F.,about 10 minutes at 300 F., and 16 to 30 seconds at 450 F. When thepolymers comprise a hydrophobic component, they may be applied inaqueous solution to a textile, leather or the like, and after curingthey may serve to impart water-repellency or -waterproofingcharacteristics depending upon the extent of hydrophobicity of thepolymer. The compounds may be applied to hydrophilic material, such ascotton and wool'to modify the physical and chemical properties thereof,either in the form of yarns or fabricsf Thus, they may modify the feel,generally improving the softness thereof; the dyeabi-lity, generallyincreasin g 'the affinity of the textile to certain types of dyes; orthey may be applied to'impart improved dimensional stability andresistance to shrinkage on Washing of the fabrics, or to increase theresistance to creasing.

For the application to textiles, the compounds of the present inventionmay be combined with auxiliary agents, such as those of aminoplasttypes, particularly the watersoluble urea-formaldehyde,triazine-formaldehyde, such as melamine-formaldehyde, heat-convertiblecondensates, especially where increased stiffness or resistance tocreasing is desired. In the following examples, which are illustrativeof the present invention, the parts and percentages are by weight unlessotherwise specified:

Example 1 (m) A solution of grams (1.1 moles) of methyl chloroacetate in300 ml. of methanol is treated slowly with stirring at 0 C. with 129grams (1.0 mole) of N-(Z- aminoethyl)-N,N'-ethyleneurea. The mixture isallowed to stir for 4 hours after the addition is completed. Theproduct, N-(2-[vmhloroacetamido]ethyl)-N,N'-ethyleneurea, is isolated byremoving solvent at reduced pressure. It is purified byrecrystallization to give a white, crystalline solid, MP. to 127 C. Itcontains 20.2% nitrogen and 17.2% chlorine by analysis which agrees withthe calculated values of 20.2 and 17.3 respectively.

(b) A solution containing 32.8 grams (0.2 mole) of a polymericN-[3-(dimethylamino)propyl]acrylarnide of equivalent weight 164 obtainedby aminolysis of poly- (methyl acrylate), 46.2 grams (0.2. mole) ofN-(Z-[achloroacetamido] ethyl)-N,N'-ethyleneurea and .134 grams ofmethanol is heated at reflux for 6 hours. The resultant product isfiltered and contained 36.2% solids, 3.3% titratable chlorine, and 6.3%nitrogen. -Calcula ted values are 3.3% chlorine and 6.42% nitrogen. v

The compound is a homopolymencomprising'units having the structure ofFormula XII:

A mixture of 182 grams of the solutionobtained after the 6 hours ofrefluxing in Example 1 and 37.5 grams of a 55% solution of formaldehydein methanol is adjusted to pH'8.5 with sodium methoxide and heated at 65P C. for 2 hours. The pH is then adjusted to 4.0 with phosphoric acidand heated at reflux for one hour. The pH is adjusted to 7.0 with sodiummethoxide and the reaction mass is filtered to clarify. The resultantsolution contains 24.6% solids, essentially the poly(methoxymethyl)derivative of the polyquaternary obtained in Example 1.

Example 3 p A mixture of 115 grams of poly(B-di-methylaminoethyl vinylether),- 300 ml. of methanol and 140 grams (a molar equivalent) of.N-methoxymethyl-u-chloroacetamide is heated at reflux for 6 hours. Theproduct is a polymer comprising units having the structure of FormulaXIII:

XIII CHzCH- H3):

OC2H4N-CH2CONHOHzOCHa 1 Example 4 The product obtained in Example 3 isdiluted with water to give a solution containing 5% of active polymericma-' terial and 0.5% by weight of solution of ammonium chloride isadded. A nylon fabric is padded through so as to retain about 35% of thequaternary in solution. The fabric is air-dried and cured for minutes at300 F. The fabric is effectively protected against the development ofstatic charge and retains this protection after five full soap washcycles in a launderometer. This treatment is similarly employed andeffective with polyester (polyethylene terephthalate), polyacrylonitrileand cellulose acetate fabrics in conferring antistatic propertiesthereto;

Example 5 (a) One mole of methyl a-chloroacetate isfreacted with onemole of -N-(3-aminopropyl)-N,N'-trimethyleneurea, which may also becalled N-(3-aminopropyl) hexahydropyridimidone-Z, by the procedure ofExample 1(a). The product isolated,N-[3-(a-ch1oroacetamido)propyl]-hexahydropyrimidone-Z, is a white,crystalline solid.

(b) To a solution of a copolymer of 30 mole percent offi-dimethylaminoethyl methacrylate with 70 mole percent of ethylacrylate in 270 grams of methanol containing 0.4 gram mole equivalent ofthe amine, 0.4 gram mole of the product of part (a) hereof .isadded andthe mixture is -heated at reflux for 7 hours, thereby producing asolution of a polymer containing 70 mole percent of ethyl acrylate unitsand 30 mole percent of units having the structure of Formula XIV:

phosphoric acid and heated at reflux for 1 hour. The pH.

is adjusted to 7 with sodium methoxide and the reaction mass is filteredto clarify it. The product is a solution containing thepoly(methoxymethyl) derivative of the polyquaternary nitrogen compoundof part (b) hereof.

Example 6 The product obtained in Example 5 (c) is diluted with water togive a solution containing 5% of active polymeric material and 0.5% byweight of a solution of ammonium chloride is added. A .nylon fabric ispadded through so as to retain about 35 of the quaternary in solution.The fabric is air-dried and cured for 10 minutesat 300 F. The 'fabric iseflectively protected against the development" of static charge andretains this protection after five full soap wash cycles in alaunderometer. This treatment is similarly employed and eifective withpolyester, polyacrylonitrile and cellulose acetate fabrics in conferringantistatic properties thereto.

- Example 7 (a) One mole of N-(fl-[a-chloroacetarrfido]ethyl)-N,N'-ethyleneurea is dissolved in 300 ml. of a 30%" solution offormaldehyde in' methanol adjusted to apHof 8.0 with sodium hydroxide.The resultant solution is heated at 55 to 60 C. for 30 minutes. About ofthe initial cyclic urea is converted to the methylol derivative'asmeasured by titration with sodium sulfite at O'to 5.

(b) To the solution obtained in part (a) there is added a copolymer ofmole percent of vinyl pyrrolidone with 5 mole percent ofZ-dimethylaminooctyl acrylate and the mixture is heated'at reflux for 6hours. The product is a copolymer of 95 mole percent of vinylpyrrolidone with 5 mole percent of units having the structure of Formula(a) 'A mixture of 5 gram moles of B-dimethylaminoethyl acrylate and 5gram moles of N-(u-chloroacetyD N,N-ethyleneurea in 2.5 liters ofmethanol is heated at reflux for 7 hours and the methanol is thenevaporated to leave the dry quaternary compound.

(b) A mixture of 25 gram moles ofB-dimethylaminoethyl acrylate and'25gram moles of benz yl chloride in 5 liters of methanol is heated atreflux for 10 hours and the methanol is evaporated to leave thequaternary compound.

I ;(c) The 5 gram moles of the quaternary of part (a) is mixed with. the25 gram moles of the quaternary of part (b) and with70 gram moles ofn-butyl acrylate. About 2%, onthe total weight of these monomers, ofazodiisobutyronitrile is added and copolymerization is effected byheating at 60 C. for 16 hours in an inert atmosphere of nitrogen.

Example 9 The procedure of Example 3 is repeated replacing the Nmethoxymethyl-a-chloroacetamide with a molar equivalent ofa-chloroacetamide itself. The productis a poly- 11 Example 10 Theprocedure of Example 9 is repeated replacing the a-chloroacetamide witha molar equivalent 'of oc-ClflOlO- acetylurea. The product is a polymerof units of Formula XVII:

XVII CHT-CH (CHO: OCtlEhN-CHzC ONHCONH:

Example 11 (a) There is charged into a reaction vessel 2,090 grams of a53.5% solution in toluene of methyl polyacrylate (13 moles) (mol Weightof 15,000 to 25,000), having a Gardner-Holdt viscosity of Z (75 poises)as a 50% solution in toluene at 25 C. Then 500 grams of toluene isremoved by stirring and heating (steam bath) the solution at reducedpressure (30 to 50 mm). To the viscous, colorless polymer solution thatremains, there is added 755 grams of dirnethylam-inopropylamine (7moles) and 200 ml. of butanol, and the mixture is heated with stirringuntil homogeneous. A solution of 200 grams of a 25% solution of sodiummethoxide in methanol methoxide on polyacr'ylate) is diluted with 200ml. of butanol and added dropwise to the hot solution. This addition isperformed slowly to avoid gelation of the polymer. The final mixture isheated to reflux for 16 hours. The copolymer in the resulting solutioncontained 43% of methyl acrylate units and 57 of 'N-(3-dim'et'nylaminOropyD-acrylamide units.

(b) The copolymer solution obtained in part (a) is diluted with 15liters of absolute ethanol and stirred at 80 C. until it is homogeneous.At this temperature, 7.5 gram moles ofN-(B-chloroethyl)-N,N'-ethyleneurea is added slowly. The resultingsolution is heated to 80 to 85 C. for about 12 hours. The quaternarycompound isolated by evaporating the solvent, slurrying the solidresidue with petroleum ether, and drying is a water5soluble light tansolid comprising methyl acrylate units and units of the Formula XVIII:

XVIII O CHr-CH (CH2):

C ONH. (C H2) NC QHAN/ NH Cl HzC-( )H2 Example 12 Example 13 (a) Theprocedure of "Example 3 is repeated replacing the vinyl other with "amolarly equivalent amount of poly-.(N-I3=dimethylaminopropyl]acrylamide). The polymer obtained comprisedunits having the structure of Formula XIX: XIX 0112-011- C ONH(CHi)-a1|T C'HzC ONHCHaO CH3 (b) The polymer of part (a) is applied tonylon,-cellulose acetate, polyethylene terephthalate (Dacron) and Ipolyacrylonitrile rabn'es (Orlo'n) by the procedure of Example 4.Effective antistatic quality of durable character is obtained.

Example 14 The eopolymers of Examples 9 and when added to 12 of 20%carbon-black water in an of 0.3% on the weight of carbon black :giveuni-term, stable dispersions.

It is to be understood that changesand variations may be made withoutdeparting from the spirit and scope of the invention as defined in theappended claims.

We claim: i

1. A monomericcompound having the formula I CHFCR R is selected from thegroup consisting of hydrogen and methyl,

Y .is selected from the group consisting of 0, -CONR-, and --COO, s A isselected from the group consisting of straightchain and branched-chainalkylene groups having 2 to 10 carbon atoms and suchalkylene groupssubstituted by at least one hydroxyl group, at leasttwo of the carbonatoms of being connected in a chain between the N atom and Y group ofthe formula, R and R are selected from the group consisting of (.17)separate groups selected individually from the group consisting ofsaturated and ethylenically unsaturated hydrocarbon groups of 1 m4carbon atoms, and '(2) a composite group which together and with theadjoining N atoms form a heterocyclic nucleus se 'lected from the groupconsisting of the .morpholino residue, the pyrrolidino residue,the'pipenidino residue, and an N-alkyl piperazino residue of the formula:(C H :NR where R is an alkyl group 0t 1 to 18 carbon atoms, X is ahalogen atom, and R is 'a radical selected from the group consisting ofthose having the Formulas II and III following:

R" is selected from the group consisting of H, -CH OH, and -'CH OR whereR is an alkyl group having from 1 to 4 carbon atoms,

p is an integer having a value of 1 to '2,

n is an integer having a value of 1 to 2 when p is 2 p 'but having onlya value of 1 when p is 1., and i Z is selected from the up consisting ofand ;CH when p is l, but is only CH when p 1s r 2. A polymer ofmonoethylenically unsaturated mono mers -comprising at least 5 molepercent of at least one monomer .as defined in claim '1.

' 3. A polymer of monoethylenicall y unsaturated mono mers comprisingatleast 5 mole percent of'at least one monomer as defined in claim 1,said polymer comprising at least 30 mole percent of units containingquaternary ammonium nitrogen.

4. A polymer of monoethylenically unsaturated monomers comprising atleast 30 mole percent of at least one monomer as defined in claim 1.

5 A polymer of monoethylenically unsaturated monowhere:

A is an alklene group having 2 to 10' carbon atoms, at least two of thecarbon atoms thereof being connected in a chain between the N and Oatoms,

, R is a saturated hydrocarbon group of 1 to 4 carbon atoms, R is asaturated hydrocarbon group of 1 to 4 carbon atoms, and X is a halogenatom.

6. A polymer of monoethylenically unsaturated monomers comprising atleast 5 mole percent of a monomer h-aving'the formula where A is analkylene group having 2 to carbon atoms, at least two' of the carbonatoms thereof being connected in a chain-between the nitrogen atoms, Ris a saturated hydrocarbon group of 1 to 4 carbon atoms, v R is asaturated hydrocarbon group of l to- 4 carbon atoms, and I v X is ahalogen atom. I

7. A polymer of monoethylenically unsaturated monomers comprising atleast 5 mole percent of a monomer having the formula A is an alkylenegroup having 2 to 10 carbon atoms,

at least two of the carbon atoms thereof being connected in a chainbetween the nitrogen atoms,

R is a saturated hydrocarbon group of l to 4 carbon atoms, I

R is a saturated hydrocarbon group of l to 4 carbon atoms,

X is a halogen atom, and I n is an integer having a value of 1 to 2.

8. A polymer containing units having the formula oomrwnnaflcmooNnozm-N111B 1 H20CH1 9. A polymer containing units having the formula CH2C(GHs) (CH3): CQOQ2H4NCH2CONH(CH2).1N

Hi I 10. A polymer containing units having the formula III wherein:

R is selected from the group consisting of H,

11. A polymer containingunits having the formula f-CH2(I H. (01192 0 ICONH(CHz)sN-C2H4N NH,

12. A method which comprises reacting, at a temperature of about 60 toC., a tertiary amine having the formula CH =C (R)YANR' R withaquaternizing agent having the formula R X't'o produce a monomer, andpolymerizing the last-mentioned'monomer at a temperatu're of about 60 to100 C., the 'sym-bolsof the formula being defined as follows:

' R is selected from the group corisistingtof hydrogen and methyl,

Y is selected from the group consisting of O,

--CONR-, and COO", A is selected from the group consisting ofstraight-chain and branched-chain alkylene groups having 2 to 10 carbonatoms and such alkylene groups substituted by at least one hydroxylgroup, at least two of the carbon atoms of A being connected in a chainbetween the N atom and Y group of the formula,

R and R are selected from the group consisting of separate saturatedhydrocarbon groups of 1 to 4 .carbon atoms, and (2) a composite group.which together and with the adjoining N atoms form a heterocyclicnucleus selected from the group consisting of the, morpholino residue,the pyrrolidino residue, the piperidino residue, and an N -alkylpiperazino residue of the formula :(C H :NR where R is an alkyl group of1 to 18 carbon atoms,

X is a halogen atom, and

R is a radical selected from the group consisting of those having theFormulas II and III following:

CH OH, and -CH OR where R is an alky group having from 1 to 4 carbonatoms,

p is in integer having a value of 1 to 2,

n is an integer having a value of 1 to 2 when p is 2 but having only avalue of 1 when p is l, and i Z is selected from the group consisting ofand CH, when p is 1, but is only CH when p is 2. 13. A methodwhichcomprises quate'rnizing a polymer of a tertiary amine having the formulaR is selected from the group consisting of hydrogen and methyl, Y

Y is selected from the group consisting of O,

vA is selected from the group consisting ofstraightchain andbranched-chain alltylene groupshaving 2 to 10 15 carbo'n atoms and suchalkylene groups substituted by at least one hydroxyl group, at least twoof the carbon atoms of A being connected in a chain between the N atomand Y group of the formula,

R and R are selected from the group consisting of separate saturatedhydrocarbon groups of 1 to 4 carbon atoms, and (2) a composite groupwhich to gether and with the adjoining N atoms form a heterocyclicnucleus selected from the group consisting of the morpholino residue,the pyrrolidino residue, the piperidino residue, and an N-alkylpiperazino residue of the formula :(C H :NR where R is an alkyl group ofl to 18 carbon atoms,

X is a halogen atom, and

R is a radical selected from the group consisting of those having theFormulas II and III following:

R" is selected from the group consisting of H, 'CH OH, and CH OR where Ris an alkyl group having from 1 to 4 carbon atoms, p is an integerhaving a value of 1 to '2, rt is an integer having a value of 1 to2'when. p is 2 but having only a value of 1 when p is 1, and Z isselected from the group consisting of I! Q and -CH when pis 1, but isonly CH when p is 2. 14. A method as defined in claim 13 which comprisesthe additional step of quaternizing, at a temperature of about 60 to 1000., additional tertiary nitrogen containing units of the polymer with acompound of the formula R X as defined hereinafter, the amount of R Xand R X being sufiicient to produce at least 30 mole percent ofquaternized units in the polymer, X being a halogen atom as before, andR being selected from the group consisting of benzyl, cyclohexyl, andalkyl groups having 1 to 4 carbon atoms.

15. A method which comprises impregnating a textile material with anaqueous dispersion of a water-soluble polymer of monoethylenicallyunsaturated monomers comprising at least mole percent of at least onemonomer having the formula I cnl=on R" R1 Y-A-N where:

Ris selected from the group consisting of hydrogen and methyl,

Y is selected from the group consisting of O,

-CONR, and --CO0--,

-I :A is selected from the group consisting of straight-chain sandbranched-chain alkylene groups having ,2 to, 10 carbon atoms and suchalkylene groups substituted by at least one hydroxyl group, at'least twoof the carbon atoms of A being connected in "a chain between the N atomand Y group of the formula, I v R and R are selected from the groupconsisting of (1) separate groups selected individually from the groupconsisting of saturated and ethylenically unsaturated hydrocarbon groups0f 1 to 4earbon'atoms, and (2) a composite group which "together andwith the adjoining N atoms form a heterocyclic "nucleusselet'ated fromthe group consisting of the inorpholino residue,

the-pyrr'olidino residue, the piperidino residue, and an N-alkylpiperazino residue of the formula X is a halogen atom, and

R is a radical selected from the group consisting of those having theFormulas II and II following:

R is selected from the group consisting of -CH OH,

and CH,,OR where R is an alkyl group having from- 1 to 4 carbon atoms, 7

p is an integer having a value of 1 to 2 n is an integer having a valueof 1 to 2 when p is 2 but having only a value of 1 when p is 1, and

Z is selected from'the group consisting of and when p is l, but is onlyCH when p is 2, and drying and heating the impregnated material at atemperature of 240 F. to 450 F.

16. A method which comprises impregnating a t extile material with anaqueous dispersion of a water-soluble polymer of monoethylenicallyunsaturated monomers comprising at least 5 mole percent of at least onemononier having the formula R is selected from the group consisting ofhydrogen and methyl,

Y is selected from the group consisting of .0,

h A is selected from the group consisting of straight-chain III andbranched-chain alkylene groups having 2 to 10 carbon atoms and suchaikylene groups substituted by at least one hydro'xyl group, at leasttwo of the carbon atoms of A being connected in a chain between the Natom and Y group of the formula,

R' and R are selected from the group consisting of (1) where R is analkyl group of 1 to 18 carbon atoms, X is a halogen atom, and R is-aradical selected from the group consisting of those having the FormulasII and III followings:

-CH CONHCONHR T CH1 wherein:

R is selected from the group consisting of --CH OH, and -CH OR where Ris an 'alkyl group having from 1 to 4 carbon atoms, 2,256,186 17 is aninteger having a value of 1 to 2, 2,511,750 n is an integer having avalue of 1 to 2 when p is 2 but 2,526,757 having only a value of 1 whenp is 1, and 2,623,224 Z is selected from the group Consisting f2,694,695 2,741,568 1 2,744,130 0 2,764,578 r and CH when p is 1, but isonly CH when p is 2,

I said polymer comprising at least 30 mole percent of units containingquaternary ammonium nitrogen,

a temperature of 240 F. to 450 F.

References Cited in the file of this patent UNITED STATES PATENTS Balleet a1 Sept. 16, 1941 Wilson Aug. 8, 1950 Larson et a1 Oct. 24, 1950Cairns et a1. Feb. .10, 1953 Bortnick Nov. 6, 1954 Hayek Apr. 10, 1956Winberg May 1, 1956 Barney Sept. 25, 1956 OTHER REFERENCES Pear-1 eta1.: J our. of The American Chem. Society, and drying and heating theimpregnated material at 15 vol. 61, pp. 1377-1378, June 1939.

1. A MONOMERIC COMPOUND HAVING THE FORMULA 